Pyritic stromatolites from the Paleoarchean Dresser Formation, Pilbara Craton: Resolving biogenicity and hydrothermally influenced ecosystem dynamics.

This study investigates the paleobiological significance of pyritic stromatolites from the 3.48 billion-year-old Dresser Formation, Pilbara Craton. By combining paleoenvironmental analyses with observations from well-preserved stromatolites in newly obtained drill cores, the research reveals stratiform and columnar to domal pyritic structures with wavy to wrinkly laminations and crest thickening, hosted within facies variably influenced by syn-depositional hydrothermal activity. The columnar and domal stromatolites occur in strata with clearly distinguishable primary depositional textures. Mineralogical variability and fine-scale interference textures between the microbialites and the enclosing sediment highlight interplays between microbial and depositional processes. The stromatolites consist of organomineralization - nanoporous pyrite and microspherulitic barite - hosting significant thermally mature organic matter (OM). This includes filamentous organic microstructures encased within nanoporous pyrite, resembling the extracellular polymeric substance (EPS) of microbes. These findings imply biogenicity and support the activity of microbial life in a volcano-sedimentary environment with hydrothermal activity and evaporative cycles. Coupled changes in stromatolite morphology and host facies suggest growth in diverse niches, from dynamic, hydrothermally influenced shallow-water environments to restricted brine pools strongly enriched in SO 4 2 - $$ {\mathrm{SO}}_4^{2-} $$ from seawater and hydrothermal activity. These observations, along with S stable isotope data indicating influence by S metabolisms, and accumulations of biologically significant metals and metalloids (Ni and As) within the microbialites, help constrain microbial processes. Columnar to domal stromatolites in dynamic, hydrothermally influenced shallow water deposits likely formed by microbial communities dominated by phototrophs. Stratiform pyritic structures within barite-rich strata may reflect the prevalence of chemotrophs near hydrothermal venting, where hydrothermal activity and microbial processes influenced barite precipitation. Rapid pyrite precipitation, a putative taphonomic process for preserving microbial remnants, is attributed to microbial sulfate reduction and reduced S sourced from hydrothermal activity. In conclusion, this research underscores the biogenicity of the Dresser stromatolites and advances our understanding of microbial ecosystems in Earth's early history.

Postprocessing Workflow for Laboratory Diffraction Contrast Tomography: A Case Study on Chromite Geomaterials.

Texture stands as a fundamental descriptor in the realms of geology and earth and planetary science. Beyond offering insights into the geological processes underlying mineral formation, its characterization plays a pivotal role in advancing engineering applications, notably in mining, mineral processing, and metal extraction, by providing quantitative data for predictive modeling. Laboratory diffraction contrast tomography (LabDCT), a recently developed 3D characterization technique, offers nondestructive measurement of grain phases including their morphology, distribution, and crystal orientation. It has recently shown its potential to assess 3D textures in complex natural rock samples. This study looks at improving on previous work by examining the artifacts and presents a novel postprocessing workflow designed to correct them. The workflow is developed to rectify inaccurate grain boundaries and interpolate partially reconstructed grains to provide more accurate results and is illustrated using multi-scan examples on chromite sands and natural chromitite from the Upper Group 2 Reef layer in South Africa. The postcorrected LabDCT results were validated through qualitative and quantitative assessment using 2D electron back-scattered diffraction on polished sample surfaces. The successful implementation of this postprocessing workflow underscores its substantial potential in achieving precise textural characterization and will provide valuable insights for both earth science and engineering applications.

Comparison of Laboratory Diffraction Contrast Tomography and Electron Backscatter Diffraction Results: Application to Naturally Occurring Chromites.

Understanding how minerals are spatially distributed within natural materials and their textures is indispensable to understanding the fundamental processes of how these materials form and how they will behave from a mining engineering perspective. In the past few years, laboratory diffraction contrast tomography (LabDCT) has emerged as a nondestructive technique for 3D mapping of crystallographic orientations in polycrystalline samples. In this study, we demonstrate the application of LabDCT on both chromite sand and a complex chromitite sample from the Merensky Reef (Bushveld Complex, South Africa). Both samples were scanned using LabDCT and Electron Backscatter Diffraction (EBSD), and the obtained results were rigorously evaluated using a comprehensive set of qualitative and quantitative characterization techniques. The quality of LabDCT results was accessed by using the "completeness" value, while the inaccuracies were thoroughly discussed, along with proposed potential solutions. The results indicate that the grain orientations obtained from LabDCT are comparable to that of 2D EBSD but have the advantage of collecting true 3D size, shape, and textural information. This study highlights the significant contribution of LabDCT in the understanding of complex rock materials from an earth science perspective, particularly in characterizing mineral texture and crystallography in 3D.

Taphonomy of microorganisms and microbial microtextures at sulfidic hydrothermal vents: A case study from the Roman Ruins black smokers, Eastern Manus Basin.

Biological activity at deep-sea hydrothermal chimneys is driven by chemotrophic microorganisms that metabolize chemicals from the venting high-temperature fluids. Understanding taphonomy and microbial microtextures in such environments is a necessity for micropaleontological and palaeoecological research. This study examines fossilized microorganisms and related microtextures in a recent black smoker from the Roman Ruins hydrothermal vent site, Eastern Manus Basin offshore of Papua New Guinea. Whereas the center of the examined sulfide chimney is dominated by high-temperature mineralogy (chalcopyrite and dendritic sphalerite), filamentous and coccoidal biomorphs occur in an outer, warm zone of mixing between hydrothermal fluids and seawater, which is indicated by their occurrence within colloform and botryoidal pyrite of barite-pyrite coprecipitates. Both morphotypes can be interpreted as thermophilic microorganisms based on their occurrence in a high-temperature habitat. Their separate (non-commensal) occurrence hints at sensitivities to microenvironmental conditions, which is expectable for strong temperature, pH, and redox gradients at the walls of deep-sea hydrothermal chimneys. Whereas both morphotypes experienced mild thermal overprint, taphonomic differences exist: (i) spaces left by cells in filamentous fossils are predominately filled by silica, whereas inter/extracellular features (crosswalls/septae and outer sheaths) are pyritized; (ii) coccoidal fossils show both silica- and pyrite-infilled interiors, and generally better preservation of cell walls. These different manifestations presumably relate to an interplay between microenvironmental and biological factors, potentially contrasting metabolisms, and differences in cell wall chemistries of distinct bacteria and/or archaea. A further hypothesis is that the coccoidal features represent biofilm-forming organisms, whose organic matter derivates contributed to the formation of intimately associated wavy and wrinkly carbonaceous laminations that are at least locally distinguishable from the texture of the surrounding pyrite. Hence, the presented data provide evidence that microtextures of microbiota from hydrothermal systems can have a similar significance for palaeobiological research as those from sedimentary environments.

Further Insights into the Performance of Silylated Polyacrylamide-Based Relative Permeability Modifiers in Carbonate Reservoirs and Influencing Factors.

We have previously used surface chemistry analysis techniques to optimize the functionalization of carbonate rocks with a silylated polyacrylamide-based relative permeability modifier (RPM). The RPM is expected to selectively reduce the permeability to water in a hydrocarbon reservoir setting, resulting in a reduction in the amount of produced water while maintaining the production of oil/gas. This study will focus on using core flooding techniques with brine/crude oil under reservoir conditions (i.e., 1500 psi pore pressure and 60 °C temperature) to understand the impact of a silylated polyacrylamide-based RPM on the fluid transport properties in carbonate rocks. The effects of RPM concentration, brine salinity, rock permeability, and pore structure on permeability characteristics were studied. Scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDX) provided visual images of the polymer adsorbed onto the rock surfaces and confirmed the attachment of the polymer on the surface of the rock pore space after treatment. The relative percentage of Si increased from 1.65 to 13.55%, and the relative percentage of N increased to 4.54%. Core flooding showed that increasing the PAM-co-AA (poly acrylamide-co-acrylic acid partial sodium salt) concentration resulted in residual resistance factors for oil (RRFoil) and brine (RRFbrine) that were greater than 1. However, there was a modest decrease in the disproportionate permeability reduction (DRP) ratio (RRFbrine/RRFoil) from 1.75 to 1.60 when the polymer concentration was increased from 0.05 to 0.1 wt %. Furthermore, the RRFbrine values decreased slightly from 120 to 62 with increasing salinity (i.e., 1-10% NaCl) because of electrostatic shielding caused by charged ions in brine and the RPM. The cross-over points of relative permeability in these four samples shifted to the right because of the larger decrease in relative water permeability compared with relative oil permeability. End-point relative permeability to water in sample C-5 decreased by 80%, showing a reduction greater than that in the sample C-2 (i.e., 74%). Kr curves indicated a stronger formation damage in sample C-1, C-2, and C-4 than in sample C-5. Rock samples with a higher initial permeability exhibited a higher RRFbrine to RRFoil ratio (i.e., 3.05) under similar test conditions. This can be attributed to a larger pore radius, which was verified by nuclear magnetic resonance (NMR) measurements. Furthermore, a detailed mechanism has been proposed to understand the effects of the RPM on fluid transport in porous carbonate cores. In this study, SEM-EDX and NMR measurements combined with core flooding tests provide insights into the performance of silylated polyacrylamide-based RPMs and benefit its future implementation in carbonate reservoirs.

Pore Structure Changes Occur During CO2 Injection into Carbonate Reservoirs.

Observations and modeling studies have shown that during CO2 injection into underground carbonate reservoirs, the dissolution of CO2 into formation water forms acidic brine, leading to fluid-rock interactions that can significantly impact the hydraulic properties of the host formation. However, the impacts of these interactions on the pore structure and macroscopic flow properties of host rock are poorly characterized both for the near-wellbore region and deeper into the reservoir. Little attention has been given to the influence of pressure drop from the near-wellbore region to reservoir body on disturbing the ionic equilibrium in the CO2-saturated brine and consequent mineral precipitation. In this paper, we present the results of a novel experimental procedure designed to address these issues in carbonate reservoirs. We injected CO2-saturated brine into a composite core made of two matching grainstone carbonate core plugs with a tight disk placed between them to create a pressure profile of around 250 psi resembling that prevailing in reservoirs during CO2 injection. We investigated the impacts of fluid-rock interactions at pore and continuum scale using medical X-ray CT, nuclear magnetic resonance, and scanning electron microscopy. We found that strong calcite dissolution occurs near to the injection point, which leads to an increase in primary intergranular porosity and permeability of the near injection region, and ultimately to wormhole  formation. The strong heterogeneous dissolution of calcite grains leads to the formation of intra-granular micro-pores. At later stages of the dissolution, the internal regions of ooids become accessible to the carbonated brine, leading to the formation of moldic porosity. At distances far from the injection point, we observed minimal or no change in pore structure, pore roughness, pore populations, and rock hydraulic properties. The pressure drop of 250 psi slightly disturbed the chemical equilibrium of the system, which led to minor precipitation of sub-micron sized calcite crystals but due to the large pore throats of the rock, these deposits had no measurable impact on rock permeability. The trial illustrates that the new procedure is valuable for investigating fluid-rock interactions by reproducing the geochemical consequences of relatively steep pore pressure gradients during CO2 injection.

Palaeobiology of red and white blood cell-like structures, collagen and cholesterol in an ichthyosaur bone.

Carbonate concretions are known to contain well-preserved fossils and soft tissues. Recently, biomolecules (e.g. cholesterol) and molecular fossils (biomarkers) were also discovered in a 380 million-year-old concretion, revealing their importance in exceptional preservation of biosignatures. Here, we used a range of microanalytical techniques, biomarkers and compound specific isotope analyses to report the presence of red and white blood cell-like structures as well as platelet-like structures, collagen and cholesterol in an ichthyosaur bone encapsulated in a carbonate concretion from the Early Jurassic (~182.7 Ma). The red blood cell-like structures are four to five times smaller than those identified in modern organisms. Transmission electron microscopy (TEM) analysis revealed that the red blood cell-like structures are organic in composition. We propose that the small size of the blood cell-like structures results from an evolutionary adaptation to the prolonged low oxygen atmospheric levels prevailing during the 70 Ma when ichthyosaurs thrived. The δ13C of the ichthyosaur bone cholesterol indicates that it largely derives from a higher level in the food chain and is consistent with a fish and cephalopod diet. The combined findings above demonstrate that carbonate concretions create isolated environments that promote exceptional preservation of fragile tissues and biomolecules.

Preparation of samples with both hard and soft phases for electron backscatter diffraction: examples from gold mineralization.

Preparation of high-quality polished sample surfaces is an essential step in the collection of microanalytical data on the microstructures of minerals and alloys. Poorly prepared samples can yield insufficient or inconsistent results and, in the case of gold, potentially no data due to the "beilby" layer. Currently, preparation of ore samples is difficult as they commonly contain both hard and soft mineral phases. The aim of our research is to produce suitably polished sample surfaces, on all phases, for electron backscatter diffraction analysis. A combination of chemical-mechanical polishing (CMP) and broad ion-beam polishing (BIBP) was used to tackle the problem. Our results show that it is critical to perform CMP first, as it produces a suitable polish on the hard mineral phases but tends to introduce more damage to the soft mineral surfaces. BIBP is essential to produce a high-quality polish to the soft phases (gold). This is a highly efficient method of sample preparation and is important as it allows the complete quantification of ore textures and all constituent mineral phases, including soft alloys.

Distribution of metals in the termite Tumulitermes tumuli (Froggatt): two types of Malpighian tubule concretion host Zn and Ca mutually exclusively.

The aim of this study was to determine specific distribution of metals in the termite Tumulitermes tumuli (Froggatt) and identify specific organs within the termite that host elevated metals and therefore play an important role in the regulation and transfer of these back into the environment. Like other insects, termites bio-accumulate essential metals to reinforce cuticular structures and utilize storage detoxification for other metals including Ca, P, Mg and K. Previously, Mn and Zn have been found concentrated in mandible tips and are associated with increased hardness whereas Ca, P, Mg and K are accumulated in Malpighian tubules. Using high resolution Particle Induced X-Ray Emission (PIXE) mapping of whole termites and Scanning Electron Microscope (SEM) Energy Dispersive X-ray (EDX) spot analysis, localised accumulations of metals in the termite T. tumuli were identified. Tumulitermes tumuli was found to have proportionally high Mn concentrations in mandible tips. Malpighian tubules had significant enrichment of Zn (1.6%), Mg (4.9%), P (6.8%), Ca (2.7%) and K (2.4%). Synchrotron scanning X-ray Fluorescence Microprobe (XFM) mapping demonstrated two different concretion types defined by the mutually exclusive presence of Ca and Zn. In-situ SEM EDX realisation of these concretions is problematic due to the excitation volume caused by operating conditions required to detect minor amounts of Zn in the presence of significant amounts of Na. For this reason, previous researchers have not demonstrated this surprising finding.